US4614646A - Stabilization of peroxide systems in the presence of alkaline earth metal ions - Google Patents
Stabilization of peroxide systems in the presence of alkaline earth metal ions Download PDFInfo
- Publication number
- US4614646A US4614646A US06/686,111 US68611184A US4614646A US 4614646 A US4614646 A US 4614646A US 68611184 A US68611184 A US 68611184A US 4614646 A US4614646 A US 4614646A
- Authority
- US
- United States
- Prior art keywords
- formula
- chelant
- alkali metal
- ammonium
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
- C01B15/01—Hydrogen peroxide
- C01B15/037—Stabilisation by additives
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3902—Organic or inorganic per-compounds combined with specific additives
- C11D3/3937—Stabilising agents
- C11D3/394—Organic compounds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
- D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
- D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
- D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
- D21C9/10—Bleaching ; Apparatus therefor
- D21C9/16—Bleaching ; Apparatus therefor with per compounds
- D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides
Definitions
- Solutions of hydrogen peroxide are utilized for bleaching cellulosic materials, e.g. paper pulps, cotton, linen, jute and the like yarns and woven materials made therefrom.
- a principal problem is the stabilization of such peroxide solutions during storage prior to and during their use in the above applications.
- Stabilizers have been used in the past, some of which perform better under acid conditions while others work better under alkaline conditions.
- Polyphosphates and dipicolinic acid or quinolinic acid will stabilize peroxy solutions in acid media, but not in alkaline solutions, especially those having a pH above 10.
- Acyltion products of phosphorous acid e.g.
- U.S. Pat. No. 3,701,825 discloses the use of ethylenediaminetetra(methylenephosphonic acid) and its salts as stabilizers for peroxy-solutions at acid or basic conditions (pH of 1.5 to 13.5). This patent also indicates that the addition of nitrate ion into the solution provides a less corrosive solution.
- chelating agents While, as noted above, various combinations of chelating agents are useful in stabilizing peroxide bleaching systems, the presence of metal ions, e.g. iron, manganese and copper, provides a catalytic effect with respect to the decomposition of the peroxide and also tends to reduce the brightness of finished mechanical pulps. While the chelants might be expected to take care of minor amounts of the metal ions, the presence of significant amounts of magnesium and/or calcium ions which may be present in the wood pulp or water or both tends to overwhelm the ability of the chelants to complex the iron, manganese and copper ions present.
- metal ions e.g. iron, manganese and copper
- An aqueous composition containing hydrogen peroxide, or a precursor which will form said peroxide in aqueous solution is inhibited from decomposition in the presence of small amounts of copper, iron, manganese or other transition metal ions and in the presence of significant amounts of alkaline earth metal ions, e.g. Ca or Mg, by the presence of a combination of inhibitors from the group including (1) aminephosphonic acids and (2) polyalkylenepolycarboxylic acids or their analogous amides and sulfonic acid derivatives thereof. Included therein are alkali metal, ammonium or amine salts of the acid radicals, namely phosphonic, carboxylic and sulfonic.
- the present invention provides for a combination stabilizing agent for aqueous peroxide solutions useful in bleaching cellulosic materials including paper pulp and other fibrous materials such as cotton, linen, jute, rayon and the like.
- the stabilizing agent is the combination of an amino phosphonic acid, e.g. diethylenetriaminepentamethylenephosphonic acid or its ammonium, alkali metal or amine salts together with a polymer of an unsaturated carboxylic acid or amide, e.g. acrylic acid or its ammonium, alkali metal or amine salts and acrylamide.
- These stabilizer combinations are effective in stabilizing peroxy-containing solutions over a wide range of pH, i.e. from about a pH of 1.0 to about 14.0.
- the useful aminophosphonic acid derivatives are those corresponding to the formula ##STR1## wherein M is independently selected from H, alkali metal, NH 4 , and an amine radical, R 1 is an aliphatic straight or branched chain, cyclic or aromatic radical having from 2 to 6 carbon atoms, n is 0 to 12, and m is 1 to 3.
- the polymeric acids and amides useful in the invention have the formulas ##STR2## wherein A is independently hydrogen or methyl, Z is independently selected from NH 2 and OM and wherein M has the aforesaid meaning and p is from about 13 to about 5,500, preferably from about 25 to about 50. wherein the Z substituents may be the same or different; and ##STR3## wherein R 2 is an alkylene radical having from 1 to 6 carbon atoms and p' is from about 5 to about 2,000, preferably 10-25, and A and M have the above indicated meanings and wherein the M substituents may be the same or different.
- Copolymers of monomers of the above formulas are also useful.
- a partially hydrolyzed polyacrylamide is effective.
- Such polymers have molecular weights of from about 1,000 to about 400,000.
- chelants are added to enhance peroxide bleaching systems, levels of chelant from 2 to 20 pounds/ton of pulp are typically used.
- the chelants referred to above are the carboxylic acid derivatives of amines, e.g. diethylenetriaminepentaacetic acid (DTPA), which are added at the pretreatment (prebleaching) stage to take metals out of the pulp.
- DTPA diethylenetriaminepentaacetic acid
- the chelant is partially removed in the subsequent dewatering step, but that which remains is rapidly destroyed in the bleaching step when contacted with the peroxide.
- the present invention adds the chelant primarily to stabilize the peroxide during the bleaching process.
- the amount of phosphonate chelant and the ratio of polymer to phosphonate needed to stabilize an alkaline-peroxide system will be directly related to the level of metals present.
- the phosphonate is added at levels sufficient to stabilize the peroxide solution by sequestering the transition metals.
- the ratio of polymer to phosphonate is dependent on the concentration of hardness ions, e.g. Ca or Mg, in the system that interfere with the phosphonate's ability to chelate the transition metals.
- concentration of hardness ions e.g. Ca or Mg
- the weight ratio in the aqueous solution of hydrogen peroxide is from about 0.05 to about 5.26 parts of phosphonic acid derivative to 1 part of polymer.
- This example compares the improved effectiveness of the phosphonate-sodium polyacrylate formulation (Runs 1 and 2) over the phosphonate or polyacrylate alone (Comp. Runs A-F) as a hydrogen peroxide stabilizer in the presence of the alkaline earth metals Ca and Mg.
- the rate of H 2 O 2 degradation was monitored under typical pulp bleaching conditions in the presence of 2.5 ppm Cu.
- the reaction mixtures were prepared using deionized water and reagent grade salts and solutions.
- the diethylenetriamine penta(methylenephosphonic acid) (DTPMP) and sodium polyacrylate (NaPA) were commercially available products.
- H 2 O 2 concentration was determined using the standard iodiometric-thiosulfate titration method.
- the DTPMP to alkaline earth metal molar ratio was 1:2. This was done to simulate conditions where the phosphonate would be overwhelmed by a relatively high concentration of the alkaline earth metals and thereby inhibit the ability of DTPMP to fully complex the trace amount of Cu or other transition metals present.
- the uncomplexed Cu could then catalyze or accelerate the H 2 O 2 decomposition rate.
- Table I A description of the components and their respective concentrations used in each run is given in Table I. The results are shown in Table II.
- the DTPMP-NaPA formulation was also a more effective peroxide stabilizer than the individual components in the presence of Mg. It is apparent from the data that the addition of Mg to the NaPA improves H 2 O 2 stability. After 30 minutes only 37.5% of the peroxide had degraded with the Mg-NaPA system (Run C) while 52.5% decomposed in the absence of Mg (Run A). When Mg was added with the DTPMP, the peroxide decomposition rate accelerated substantially. After 140 minutes in the absence of Mg (Run D) only 7.5% of the peroxide had decomposed while 45% decomposed in the presence of both Mg and DTPMP (Run F). The addition of NaPA to the Mg-DTPMP mixture (Run 1) substantially reduced the degradation rate. Again after 140 minutes, only 25% of the peroxide had been consumed. This represents about a 45% improvement over the Mg-DTPMP system.
- Example 1 In the manner of Example 1 other experiments were performed in which the ratio of phosphonate and polyacrylate were varied. The conditions for these runs were as follows:
Abstract
An aqueous composition containing hydrogen peroxide, or a precursor which will form said peroxide in aqueous solution, is inhibited from decomposition in the presence of small amounts of copper, iron, manganese or other transition metal ions and in the presence of significant amounts of alkaline earth metal ions, e.g. Ca or Mg, by the presence of a combination of inhibitors one being from the group consisting of alkyleneaminephosphonic acids and the other being from the group consisting of polyalkylenepolycarboxylic acids and their analogous amides and sulfonic acid derivatives.
Description
Solutions of hydrogen peroxide are utilized for bleaching cellulosic materials, e.g. paper pulps, cotton, linen, jute and the like yarns and woven materials made therefrom. A principal problem is the stabilization of such peroxide solutions during storage prior to and during their use in the above applications. Stabilizers have been used in the past, some of which perform better under acid conditions while others work better under alkaline conditions. Polyphosphates and dipicolinic acid or quinolinic acid will stabilize peroxy solutions in acid media, but not in alkaline solutions, especially those having a pH above 10. Acyltion products of phosphorous acid, e.g. the reaction product with organic acid anhydrides, such as propionic, butyric or caproic anhydrides, or acid chlorides, such as acetyl chloride, have been disclosed as useful in stabilizing H2 O2 solutions at pH 10 and above in U.S. Pat. No. 3,122,417. Other phosphonic acid derivatives including amino tri(methylphosphonic acid) and amino tri(ethylidenephosphonic acid) and other like ammonia derived organo phosphonic acids and their salts are disclosed as useful in stabilizing peroxy solutions at alkaline pH conditions in U.S. Pat. No. 3,234,140.
A later patent, U.S. Pat. No. 3,701,825, discloses the use of ethylenediaminetetra(methylenephosphonic acid) and its salts as stabilizers for peroxy-solutions at acid or basic conditions (pH of 1.5 to 13.5). This patent also indicates that the addition of nitrate ion into the solution provides a less corrosive solution.
Bleaching of cellulosic fibers has in the past been conducted with hydrogen peroxide, employing sodium silicate as a stabilizer, but this system results in problems when insoluble silicates are deposited upon the fibers and the machinery employed. When deposited on kraft paper fibers the result is a harsher feel of the paper. The fouling of equipment can cause down-time and shortened life of the equipment. Because of this, silicate-free systems have been suggested.
These silicate-free systems have been found to work well when magnesium salts are preset and, where high amounts of peroxide are employed, the addition of poly-(α-hydroxyacrylate) as a stabilizer is useful.* The presence of the polyacrylate also improves the brightness (See British Pat. No. 1,425,307).
In U.S. Pat. No. 3,860,391 the bleaching of cellulose fibers and mixtures of these with synthetic fibers is accomplished by employing peroxide in a silicate-free system in the presence of an aliphatic hydroxy compound, an amino alkylenephosphonic acid compound and, alternatively, with the addition of a polyaminocarboxylic acid. Representative of the above are erythritol or pentaerythritol, ethylene diaminotetra(methylenephosphonic acid) of 1-hydroxypropane-1,1,3-triphosphonic acid and ethylenediaminotetraacetic acid or nitrilotriacetic acid, respectively.
Another patent, U.S. Pat. No. 4,238,282, describes a pulp bleaching system employing chlorine (not peroxide) which uses various chelating agents, including polyacrylic acid (mol. wt.<2000), alkylene polyaminocarboxylic acids, and aminophosphonic acids and their salts.
Other more recent U.S. patents which employ such phosphonates as indicated above, but in a peroxide bleaching system, include U.S. Pat. No. 4,239,643 and U.S. Pat. No. 4,294,575.
While, as noted above, various combinations of chelating agents are useful in stabilizing peroxide bleaching systems, the presence of metal ions, e.g. iron, manganese and copper, provides a catalytic effect with respect to the decomposition of the peroxide and also tends to reduce the brightness of finished mechanical pulps. While the chelants might be expected to take care of minor amounts of the metal ions, the presence of significant amounts of magnesium and/or calcium ions which may be present in the wood pulp or water or both tends to overwhelm the ability of the chelants to complex the iron, manganese and copper ions present.
Certain combinations of the aminephosphonates together with polycarboxylic acids or polycarboxylic amides or a sulfonic acid derivative of a polyamide have now been found to provide stabilization in the presence of significant amounts of magnesium and/or calcium ions and in the presence of small amounts of copper ions and the like which catalyze the peroxide decomposition.
An aqueous composition containing hydrogen peroxide, or a precursor which will form said peroxide in aqueous solution, is inhibited from decomposition in the presence of small amounts of copper, iron, manganese or other transition metal ions and in the presence of significant amounts of alkaline earth metal ions, e.g. Ca or Mg, by the presence of a combination of inhibitors from the group including (1) aminephosphonic acids and (2) polyalkylenepolycarboxylic acids or their analogous amides and sulfonic acid derivatives thereof. Included therein are alkali metal, ammonium or amine salts of the acid radicals, namely phosphonic, carboxylic and sulfonic.
The present invention provides for a combination stabilizing agent for aqueous peroxide solutions useful in bleaching cellulosic materials including paper pulp and other fibrous materials such as cotton, linen, jute, rayon and the like. The stabilizing agent is the combination of an amino phosphonic acid, e.g. diethylenetriaminepentamethylenephosphonic acid or its ammonium, alkali metal or amine salts together with a polymer of an unsaturated carboxylic acid or amide, e.g. acrylic acid or its ammonium, alkali metal or amine salts and acrylamide. These stabilizer combinations are effective in stabilizing peroxy-containing solutions over a wide range of pH, i.e. from about a pH of 1.0 to about 14.0.
The useful aminophosphonic acid derivatives are those corresponding to the formula ##STR1## wherein M is independently selected from H, alkali metal, NH4, and an amine radical, R1 is an aliphatic straight or branched chain, cyclic or aromatic radical having from 2 to 6 carbon atoms, n is 0 to 12, and m is 1 to 3.
The polymeric acids and amides useful in the invention have the formulas ##STR2## wherein A is independently hydrogen or methyl, Z is independently selected from NH2 and OM and wherein M has the aforesaid meaning and p is from about 13 to about 5,500, preferably from about 25 to about 50. wherein the Z substituents may be the same or different; and ##STR3## wherein R2 is an alkylene radical having from 1 to 6 carbon atoms and p' is from about 5 to about 2,000, preferably 10-25, and A and M have the above indicated meanings and wherein the M substituents may be the same or different.
Copolymers of monomers of the above formulas are also useful. Thus a partially hydrolyzed polyacrylamide is effective. Such polymers have molecular weights of from about 1,000 to about 400,000.
In the pulp and paper industry where chelants are added to enhance peroxide bleaching systems, levels of chelant from 2 to 20 pounds/ton of pulp are typically used. The chelants referred to above are the carboxylic acid derivatives of amines, e.g. diethylenetriaminepentaacetic acid (DTPA), which are added at the pretreatment (prebleaching) stage to take metals out of the pulp. The chelant is partially removed in the subsequent dewatering step, but that which remains is rapidly destroyed in the bleaching step when contacted with the peroxide. The present invention adds the chelant primarily to stabilize the peroxide during the bleaching process.
The amount of phosphonate chelant and the ratio of polymer to phosphonate needed to stabilize an alkaline-peroxide system will be directly related to the level of metals present. The phosphonate is added at levels sufficient to stabilize the peroxide solution by sequestering the transition metals. The ratio of polymer to phosphonate is dependent on the concentration of hardness ions, e.g. Ca or Mg, in the system that interfere with the phosphonate's ability to chelate the transition metals. Below is a table showing recommended levels of phosphonate and polymer to be used in such systems at different levels of water hardnesses and transition metal content.
______________________________________
Wt. %
(in Aqueous H.sub.2 O.sub.2)
Wt. %
Phosphonic Acid
(in Aqueous
Derivative H.sub.2 O.sub.2) Polymer
______________________________________
(a) Low transition metals
0.1 wt. % 0.19 wt. %
(2#/ton chelant)
(b) Low hardness*
(110 ppm)
(a) High transition metals
1.0 wt. % 0.19 wt. %
(20#/ton chelant)
(b) Low hardness
(110 ppm)
(a) Low transition metals
0.1 wt. % 1.9 wt. %
(2#/ton chelant)
(b) High hardness*
(1100 ppm)
(a) High transition metals
1.0 wt. % 1.9 wt. %
(20#/ton chelant)
(b) High hardness
(1100 ppm)
______________________________________
*Low hardness is any concentration of hardness (measured as CaCO.sub.3)
below about 150 ppm and high hardness is 250 ppm and above.
According to the above table the weight ratio in the aqueous solution of hydrogen peroxide is from about 0.05 to about 5.26 parts of phosphonic acid derivative to 1 part of polymer.
This example compares the improved effectiveness of the phosphonate-sodium polyacrylate formulation (Runs 1 and 2) over the phosphonate or polyacrylate alone (Comp. Runs A-F) as a hydrogen peroxide stabilizer in the presence of the alkaline earth metals Ca and Mg. The rate of H2 O2 degradation was monitored under typical pulp bleaching conditions in the presence of 2.5 ppm Cu.
This decomposition study was conducted using a 1-liter resin kettle equipped with a 1-foot condenser, pH probe/meter, sampling tube, thermometer and magnetic stirrer. The reactor was sealed with the condenser being the only opening to the outside atmosphere. The reaction mixture was constantly agitated and the temperature maintained at 65.0°±0.2° C. by use of a circulating water bath in which the reactor kettle was partially submerged.
The reaction mixtures were prepared using deionized water and reagent grade salts and solutions. The diethylenetriamine penta(methylenephosphonic acid) (DTPMP) and sodium polyacrylate (NaPA) were commercially available products.
To the water was added the DTPMP and/or NaPA, then the Ca or Mg. After which the 2.5 ppm Cu was added and the appropriate amount of NaOH to obtain a final pH of 10.5±0.1. This solution was then transferred to the resin kettle in which it was heated. After the reaction mixture reached 65° C., the H2 O2 was added.
Periodically, during each rung, the run time, temperature, pH and H2 O2 concentration were measured and recorded. The samples taken for H2 O2 determination were first mixed with a 5 weight percent H2 SO4 solution to arrest further H2 O2 decomposition. Then the H2 O2 concentration was determined using the standard iodiometric-thiosulfate titration method.
To determine the degree of peroxide stabilization accounted for by each component of the DTPMP-NaPA formulation in the presence of the alkaline earth metals Ca and Mg, eight separate runs were conducted.
For the study, the DTPMP to alkaline earth metal molar ratio was 1:2. This was done to simulate conditions where the phosphonate would be overwhelmed by a relatively high concentration of the alkaline earth metals and thereby inhibit the ability of DTPMP to fully complex the trace amount of Cu or other transition metals present. The uncomplexed Cu could then catalyze or accelerate the H2 O2 decomposition rate. A description of the components and their respective concentrations used in each run is given in Table I. The results are shown in Table II.
TABLE I
__________________________________________________________________________
CONCENTRATIONS (WT. %)
Component
Run A
Run B
Run C
Run D
Run E
Run F
Run 1
Run 2
__________________________________________________________________________
DTPMP -- -- -- 0.15 0.15 0.15 0.15 0.15
NaPA 0.09 0.09 0.09 -- -- -- 0.09 0.09
CaCl.sub.2
-- 0.12 -- -- 0.12 -- 0.12 --
MgSO.sub.4
-- -- 0.16 -- -- 0.16 -- 0.16
CuCl.sub.2 (as Cu)
2.5 ppm
2.5 ppm
2.5 ppm
2.5 ppm
2.5 ppm
2.5 ppm
2.5 ppm
2.5 ppm
H.sub.2 O.sub.2
0.40 0.40 0.40 0.40 0.40 0.40 0.40 0.40
__________________________________________________________________________
TABLE II
__________________________________________________________________________
EFFECTS OF Ca and Mg ON THE H.sub.2 O.sub.2 STABILIZING
ABILITY OF DTPMP AND NaPA (IN THE PRESENCE OF 2.5 ppm Cu)
Run A
Run B
Run C
Run D
Run E
Run F
Run 1
Run 2
__________________________________________________________________________
Ca (moles/mole DTPMP)
-- 2 -- -- 2 -- 2 --
Mg (moles/mole DTPMP)
-- -- 2 -- -- 2 -- 2
NaPA (g/l) 4.4
4.4
4.4
-- -- -- 4.4 4.4
DTPMP (g/l) -- -- -- 4.4 4.4 4.4 4.4 4.4
Run Time Percent H.sub.2 O.sub.2 Degraded
(Minutes)
5 10.0
12.5
7.5
0.0 2.5 2.5 0.0 0.0
10 17.5
30.0
15.0
2.5 5.0 2.5 2.5 2.5
20 35.0
50.0
25.0
2.5 5.0 5.0 2.5 5.0
30 52.5
-- 37.5
2.5 5.0 12.5
5.0 7.5
60 -- -- -- 5.0 12.5
25.0
7.5 10.0
90 -- -- -- 5.0 17.5
32.5
7.5 15.0
140 -- -- -- 7.5 27.5
45.0
10.0
25.0
200 -- -- -- 10.0
-- -- -- 37.5
__________________________________________________________________________
The results demonstrate that in the presence of excess Ca, the DTPMP-NaPA formulation is substantially more effective as a peroxide stabilizer than is DTPMP or NaPA. It is apparent that NaPA is relatively ineffective as an H2 O2 stabilizer (Run A). Within 30 minutes over half of the H2 O2 had decomposed. When Ca is added along with the NaPA (Run B) the H2 O2 decomposition rate appears to accelerate somewhat. DTPMP, on the other hand, was very effective in stabilizing H2 O2 in the absence of Ca. In 200 minutes only 10% of the H2 O2 had decomposed (Run D). But when 2 moles of Ca were added per mole of DTPMP, the H2 O2 degradation rate increased rapidly to where almost 30% of the H2 O2 was consumed in only 140 minutes (Run E). Then finally, when the Ca was added to the DTPMP-NaPA combination the rate of H2 O2 degradation was reduced by over 60% (Run 1 ). In 140 minutes only 10.0% of the H2 O2 was consumed.
The DTPMP-NaPA formulation was also a more effective peroxide stabilizer than the individual components in the presence of Mg. It is apparent from the data that the addition of Mg to the NaPA improves H2 O2 stability. After 30 minutes only 37.5% of the peroxide had degraded with the Mg-NaPA system (Run C) while 52.5% decomposed in the absence of Mg (Run A). When Mg was added with the DTPMP, the peroxide decomposition rate accelerated substantially. After 140 minutes in the absence of Mg (Run D) only 7.5% of the peroxide had decomposed while 45% decomposed in the presence of both Mg and DTPMP (Run F). The addition of NaPA to the Mg-DTPMP mixture (Run 1) substantially reduced the degradation rate. Again after 140 minutes, only 25% of the peroxide had been consumed. This represents about a 45% improvement over the Mg-DTPMP system.
In the manner of Example 1 other experiments were performed in which the ratio of phosphonate and polyacrylate were varied. The conditions for these runs were as follows:
Run time˜4 hours
Temperature--65° C.
______________________________________
Initial Conditions:
______________________________________
wt. % H.sub.2 O.sub.2
0.4
wt. % CaCl.sub.2
0.12*
ppm Cu.sup.++ 2.5
pH 10.5 ± 0.2
______________________________________
*Hardness expressed as CaCO.sub.3 is 1100 ppm.
Results with respect to decomposition of peroxide are given in Table III.
______________________________________
III. VARYING THE RATIO OF DTPMP TO NaPA
DTPMP:NaPA
Ratio Actual Percent Peroxide Decomposition After
(Wt.) ppm 1 Hr. 2 Hrs.
3 Hrs. 4 Hrs.
______________________________________
-- 0:1320 100% -- -- --
1.6:2 1055:1320
100% -- -- --
-- 2110:0 14% 40% 85% 100%
3.2:1 2110:660 14% 40% 85% 100%
6.4:2 4220:1320
14% 20% 25% 27%
3.2:2 2110:1320
8% 11% 19% 23%
3.2:6 2110:3960
7% 9% 12% 18%
3.2:10
2110:6600
7% 9% 12% 18%
______________________________________
Another series of runs was made employing the same conditions as in Example 2 in which the molecular weight of the polyacrylate used was varied. Results are shown in Table IV.
______________________________________
IV. VARYING THE SODIUM POLYACRYLATE
MOLECULAR WEIGHT
Tested polymers between 1,000 and
400,000 molecular weight units. The
weight ratio of DTPMP to NaPA was 3.2:6
(2110/3960 ppm)
NaPA
Molecular Percent H.sub.2 O.sub.2 Degradation After
Weight 1 Hour 2 Hours 3 Hours
4 Hours
______________________________________
1,000 8% 14% 17% 20%
2,000 4% 6% 7% 8%
12,000 6% 8% 10% 11%
60,000 4% 6% 7% 8%
190,000 4% 6% 7% 8%
400,000 6% 8% 10% 11%
______________________________________
Other phosphonates and other polymers of unsaturated acids were employed. Results as shown in Table V.
______________________________________
V. OTHER PHOSPHONATES AND POLYMERS
Wt. Percent Peroxide
Composi- Ra- Decomposition After
tion tio ppm 1 Hr.
2 Hrs.
3 Hrs.
4 Hrs.
______________________________________
DTPMP:NaPA
3.2:2 2110:1320
8% 11% 19% 23%
DTPMP:NaPA
3.2:6 2110:3960
7% 9% 12% 18%
TTHMP:NaPA
3.2:6 2110:3960
7% 9% 12% 18%
DTPMP:PAAm
3.2:2 2110:1320
8% 11% 13% 15%
DTPMP:AMPS
3.2:2 2110:1320
7% 9% 12% 15%
______________________________________
NaPA = 2,000 mw
AMPS (sulfonic acid derivative of a polyacrylamide) = 4,000 mw
PAAm (polyacrylamide) = 3,500 mw
TTHMP = triethylenetetraminehexa(methylenephosphonic acid).
It is to be noted that the more dilute the solution of peroxide, the more stabilizer is required. Thus, the amounts of stabilizer required to stabilize concentrated solutions, e.g. 50-70% H2 O2, will be insufficient to stabilize and prevent the decomposition of H2 O2 when diluted for use. If this is not taken into consideration when the concentrated solutions are prepared, more stabilizer will need to be added when these solutions are diluted for use in bleaching.
Claims (20)
1. In a method of inhibiting decomposition of hydrogen peroxide in aqueous solution wherein a chelant is employed the improvement which consists essentially of adding to said solution
(a) an aminophosphonic acid chelant or an ammonium, alkali metal or amine salt thereof together with
(b) at least one polymer of
(1) an unsaturated carboxylic acid or an ammonium, alkali metal or amine salt thereof,
(2) an unsaturated carboxylic amide or
(3) an unsaturated carboxylic amide wherein the amide hydrogens are substituted with an alkylsulfonic acid group or an ammonium, alkali metal or amine salt thereof
and wherein the (b) additive may contain a combination of said functional groups.
2. The method of claim 1 wherein the aminophosphonic acid chelant has the formula ##STR4## wherein M is independently selected from H, alkali metal, NH4, or an amine radical, R1 is an aliphatic straight or branched chain, cyclic or aromatic radical having from 2 to 6 carbon atoms, n is 0 to 12, and m is 1 to 3.
3. The method of claim 2 wherein the polymer contains monomer units having the formula ##STR5## wherein A is independently hydrogen or methyl, Z is independently selected from NH2 and OM and wherein M is independently selected from hydrogen, an alkali metal, ammonium and an amine radical and p is from about 13 to about 5,500 or ##STR6## wherein R2 is an alkylene radical from 1 to 6 carbon atoms and p' is from about 5 to about 2,000, and mixtures thereof and A and M have the aforesaid meanings.
4. The method of claim 3 wherein the aminophosphonic acid chelant has the formula wherein R1 is ethylene, m is 1 and n is 2 and the polycarboxylic acid has the formula wherein p is an integer of from about 25 to about 50.
5. The method of claim 3 wherein the aminophosphonic acid chelant has the formula wherein R1 is ethylene, m is 1 and n is 2 and the polycarboxylic sulfonamide has the formula wherein R2 is an alkylene radical having 4 carbon atoms and p' is an integer of from about 10 to about 25.
6. The method of claim 3 wherein the aminophosphonic acid chelant has the formula wherein m is 1 and n is 0 and the polycarboxylic acid has the formula wherein p is an integer of from about 25 to about 50.
7. The method of claim 3 wherein the aminophosphonic acid chelant has the formula wherein m is 1 and n is 0 and the polycarboxylic sulfonamide has the formula wherein R2 is an alkylene radical having 4 carbon atoms and p' is an integer of from about 10 to about 25.
8. The method of claim 3 wherein the aminophosphonic acid chelant has the formula wherein R1 is ethylene, m is 1 and n is 3 and the polycarboxylic acid has the formula wherein p is an integer of from about 25 to about 50.
9. The method of claim 3 wherein the aminophosphonic acid chelant has the formula wherein R1 is ethylene, m is 1 and n is 3 and the polycarboxylic sulfonamide has the formula wherein R2 is an alkylene radical having 4 carbon atoms and p' is an integer of from about 10 to about 25.
10. The method of claim 3 wherein the weight ratio of additives in the aqueous hydrogen peroxide is from about 0.05 to about 5.3 parts of aminophosphonic acid chelant to one part of polymer.
11. The method of claim 10 wherein the water employed in the hydrogen peroxide solution has low hardness and the weight ratio of chelant to polymer is from about 0.53 to about 5.3 to one.
12. The method of claim 10 wherein the water employed in the hydrogen peroxide solution has high hardness and the weight ratio of chelant to polymer is from about 0.05 to about 0.52 to one.
13. An inhibited aqueous hydrogen peroxide composition which contains as inhibitor the combination consisting essentially of
(a) an aminophosphonic acid chelant or an ammonium, alkali metal or amine salt thereof and
(b) at least one polymer of
(1) an unsaturated carboxylic acid or an ammonium, alkali metal or amine salt thereof,
(2) an unsaturated carboxylic amide or
(3) an unsaturated carboxylic amide wherein the amide hydrogens are substituted with an alkylsulfonic acid group or an ammonium, alkali metal or amine salt thereof
and wherein the (b) additive may contain a combination of said functional groups.
14. The composition of claim 13 wherein the aminophosphonic acid chelant has the formula ##STR7## wherein M is independently selected from H, alkali metal, NH4, and an amine radical, R1 is aliphatic straight or branched chain, cyclic or aromatic radical having from 2 to 6 carbon atoms, n is 0 to 12, and m is 1 to 3 and the polymer contains monomer units having the formulas ##STR8## wherein A is independently hydrogen or methyl, Z is independently selected from NH2 and OM and wherein M is independently selected from hydrogen, an alkali metal, ammonium and an amine radical and p is from about 13 to about 5,500 or ##STR9## wherein R2 is an alkylene radical having from 1 to 6 carbon atoms and p' is from about 5 to about 2,000, and mixtures thereof and A and M have the aforesaid meanings.
15. The composition of claim 14 wherein the weight ratio of additives is from about 0.05 to about 5.3 parts of aminophosphonic acid chelant to one part of polymer.
16. The composition of claim 14 wherein the weight percent of aminophosphonic acid chelant is from 0.1 to 1.0 and of polymer is from 0.19 to 1.9.
17. An aqueous hydrogen peroxide composition inhibited against decomposition and suitable for adding to a bleaching bath useful in bleaching cellulosic products which consists essentially of
(a) from about 5 to about 70 weight percent hydrogen peroxide,
(b) from about 2.5 to about 0.025 percent of an aminophosphonic acid chelant or an ammonium, alkali metal or amine salt thereof and
(c) at least one polymer of
(1) an unsaturated carboxylic acid or an ammonium, alkali metal or amine salt thereof,
(2) an unsaturated carboxylic amide or
(3) an unsaturated carboxylic amide wherein the amide hydrogens are substituted with an alkylsulfonic acid group or an ammonium, alkali metal or amine salt thereof
and wherein the (c) additive may contain a combination of said functional groups.
18. The composition of claim 17 wherein the aminophosphonic acid chelant has the formula ##STR10## wherein M is independently selected from H, alkali metal, NH4, and an amine radical, R1 is an aliphatic straight or branched chain, cyclic or aromatic radical having from 2 to 6 carbon atoms, n is 0 to 12, and m is 1 to 3 and the polymer contains monomer units having the formulas ##STR11## wherein A is independently hydrogen or methyl, Z is independently selected from NH2 and OM and wherein M is independently selected from hydrogen, an alkali metal, ammonium and an amine radical and p is from about 13 to about 5,500 or ##STR12## wherein R2 is an alkylene radical having from 1 to 6 carbon atoms and p' is from about 5 to about 2,000, and mixtures thereof and A and M have the aforesaid meanings.
19. The composition of claim 18 wherein the aminophosphonic acid chelant has the formula wherein R1 is ethylene, m is 1 and n is 2 and the polycarboxylic acid has the formula wherein p is an integer of from about 25 to about 50.
20. The composition of claim 18 wherein the aminophosphonic acid chelant has the formula wherein R1 is ethylene, m is 1 and n is 2 and the polycarboxylic sulfonamide has the formula wherein R2 is an alkylene radical having 4 carbon atoms and p' is an integer of from about 10 to about 25.
Priority Applications (13)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/686,111 US4614646A (en) | 1984-12-24 | 1984-12-24 | Stabilization of peroxide systems in the presence of alkaline earth metal ions |
| CA000496865A CA1235881A (en) | 1984-12-24 | 1985-12-04 | Stabilization of peroxide systems in the presence of alkaline earth metal ions |
| AR302499A AR240302A1 (en) | 1984-12-24 | 1985-12-06 | A STABILIZED AQUEOUS HYDROGEN PEROXIDE COMPOSITION AND PROCEDURE FOR ITS PREPARATION. |
| EP85308960A EP0186990B1 (en) | 1984-12-24 | 1985-12-10 | Improved stabilization of peroxide systems in the presence of alkaline earth metal ions |
| DE8585308960T DE3584669D1 (en) | 1984-12-24 | 1985-12-10 | STABILIZATION OF PEROXIDE SYSTEMS IN THE PRESENCE OF EARTH ALKALINE METALS. |
| NZ214537A NZ214537A (en) | 1984-12-24 | 1985-12-12 | Stabilised aqueous hydrogen peroxide solutions |
| AU51256/85A AU576280B2 (en) | 1984-12-24 | 1985-12-16 | Inhibition of decomposition of hydrogen peroxide systems |
| ZA859707A ZA859707B (en) | 1984-12-24 | 1985-12-19 | Stabilization of peroxide systems in the presence of alkaline earth metal ions |
| NO855253A NO168940C (en) | 1984-12-24 | 1985-12-23 | INHIBITOR FOR INHIBITION OF DIVISION OF Aqueous HYDROGEN PEROX MIXTURE AND INHIBITED Aqueous HYDROGEN PEROX MIXTURE |
| JP60288047A JPS61155208A (en) | 1984-12-24 | 1985-12-23 | Improvement in stability of peroxide system in presence of alkali earth metal ion |
| DK604285A DK167491B1 (en) | 1984-12-24 | 1985-12-23 | INHIBITOR FOR INHIBITION OF DIVISION OF Aqueous HYDROGEN PEROXIDE MIXTURE AND INHIBITED Aqueous HYDROGEN PEROXIDE MIXTURE |
| BR8506446A BR8506446A (en) | 1984-12-24 | 1985-12-23 | AQUEOUS COMPOSITION OF HYDROGEN PEROXIDE, PROCESS TO INHIBIT THE DECOMPOSITION OF HYDROGEN PEROXIDE AND PROCESS FOR THE PREPARATION OF A COMPOSITION |
| FI855151A FI79825C (en) | 1984-12-24 | 1985-12-23 | INHIBERAT VATTENHALTIG KOMPOSITION AV VAETEPEROXID. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/686,111 US4614646A (en) | 1984-12-24 | 1984-12-24 | Stabilization of peroxide systems in the presence of alkaline earth metal ions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US4614646A true US4614646A (en) | 1986-09-30 |
Family
ID=24754964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/686,111 Expired - Lifetime US4614646A (en) | 1984-12-24 | 1984-12-24 | Stabilization of peroxide systems in the presence of alkaline earth metal ions |
Country Status (13)
| Country | Link |
|---|---|
| US (1) | US4614646A (en) |
| EP (1) | EP0186990B1 (en) |
| JP (1) | JPS61155208A (en) |
| AR (1) | AR240302A1 (en) |
| AU (1) | AU576280B2 (en) |
| BR (1) | BR8506446A (en) |
| CA (1) | CA1235881A (en) |
| DE (1) | DE3584669D1 (en) |
| DK (1) | DK167491B1 (en) |
| FI (1) | FI79825C (en) |
| NO (1) | NO168940C (en) |
| NZ (1) | NZ214537A (en) |
| ZA (1) | ZA859707B (en) |
Cited By (56)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4732650A (en) * | 1986-09-15 | 1988-03-22 | The Dow Chemical Company | Bleaching of cellulosic pulps using hydrogen peroxide |
| US4744968A (en) * | 1985-09-03 | 1988-05-17 | Technicon Instruments Corporation | Stabilized aqueous hydrogen peroxide solution |
| US4849198A (en) * | 1987-06-19 | 1989-07-18 | Degussa Aktiengesellschaft | Method of reducing the tendency of particulate active oxygen compounds to cake |
| US4880566A (en) * | 1985-12-23 | 1989-11-14 | Henkel Kommanditgesellschaft Auf Aktien | Silicate-and magnesium-free stabilizer mixtures |
| US4889689A (en) * | 1986-10-14 | 1989-12-26 | Ciba-Geigy Corporation | Method of disinfecting a soft contact lens with a diethylene triamine penta(methylenephosphonic acid) stabilized hydrogen peroxide solution |
| US4959075A (en) * | 1985-12-23 | 1990-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Silicate- and magnesium-free stabilizer hydrogen peroxide mixtures for bleaching processes |
| US4963157A (en) * | 1987-04-17 | 1990-10-16 | Nippon Peroxide Co., Ltd. | Method for bleaching cellulosic fiber material with hydrogen peroxide |
| US5013404A (en) * | 1989-11-15 | 1991-05-07 | The Dow Chemical Company | Process for alkaline peroxide bleaching of wood pulp using a quaternary amine as additive |
| US5102575A (en) * | 1988-06-13 | 1992-04-07 | Atochem | Stabilization of H2 O2 bleaching and bleaching/desizing baths |
| DE4035813A1 (en) * | 1990-11-10 | 1992-05-14 | Akzo Gmbh | OXYGEN BLEACHING |
| US5130053A (en) * | 1989-11-09 | 1992-07-14 | Interox Chemicals Limited | Stabilization of concentrated hydrogen peroxide solutions |
| US5145558A (en) * | 1989-11-15 | 1992-09-08 | The Dow Chemical Company | Composition for alkaline peroxide bleaching of wood pulp using a quaternary amine as additive |
| US5180514A (en) * | 1985-06-17 | 1993-01-19 | The Clorox Company | Stabilizing system for liquid hydrogen peroxide compositions |
| US5205907A (en) * | 1991-11-25 | 1993-04-27 | Macmillan Bloedel Limited | Removal of manganese from pulp using a chelating agent and magnesium sulphate |
| US5223091A (en) * | 1991-11-25 | 1993-06-29 | Macmillan Bloedel Limited | Method of brightening mechanical pulp using silicate-free peroxide bleaching |
| US5248389A (en) * | 1992-03-18 | 1993-09-28 | Fmc Corporation | Process for peroxide bleaching of mechanical pulp using sodium carbonate and non-silicate chelating agents |
| US5292449A (en) * | 1992-11-24 | 1994-03-08 | Akzo Nv | Scale inhibiting composition |
| US5302311A (en) * | 1991-02-28 | 1994-04-12 | Mitsubishi Gas Chemical Company, Inc. | Cleaning solution of semiconductor substrate |
| WO1995029216A1 (en) * | 1994-04-20 | 1995-11-02 | The Procter & Gamble Company | Detergent powder compositions comprising metal ion-chelant complex and anionic functional polymer |
| US5576028A (en) * | 1988-08-04 | 1996-11-19 | Ciba Geigy Corporation | Method of preserving ophthalmic solutions and compositions therefor |
| US5780419A (en) * | 1994-04-20 | 1998-07-14 | The Procter & Gamble Company | Detergent powder compositions comprising metal ion-chelant complex and anionic functional polymer |
| WO1999009244A1 (en) * | 1997-08-14 | 1999-02-25 | Takashi Watanabe | Chemical method for lignin depolymerization |
| US6120554A (en) * | 1998-02-02 | 2000-09-19 | American Renewable Resources Llc | Catalyzed alkaline hydrogen peroxide bleaching of dye-containing cellulose textiles |
| WO2002058660A1 (en) * | 2001-01-26 | 2002-08-01 | L'oreal | Oxidising composition for the treatment of keratin comprising a cationic poly(vinyllactam) |
| WO2003059069A1 (en) * | 2002-01-18 | 2003-07-24 | Novartis Ag | Methods for preserving ophthalmic solutions and preserved ophtalmic solutions |
| US6645450B2 (en) * | 2000-03-03 | 2003-11-11 | Steen Research, Llc | Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters |
| US20040101461A1 (en) * | 2002-11-22 | 2004-05-27 | Lovetro David C. | Chemical composition and method |
| US20050217813A1 (en) * | 2004-03-31 | 2005-10-06 | Shevchenko Sergey M | Methods to enhance brightness of pulp and optimize use of bleaching chemicals |
| US20070048388A1 (en) * | 2005-08-26 | 2007-03-01 | Fu-Pao Tsao | Stabilized and preserved ketotifen ophthalmic compositions |
| US20070048389A1 (en) * | 2005-08-26 | 2007-03-01 | Fu-Pao Tsao | Stabilized and preserved ketotifen ophthalmic compositions |
| US20070059229A1 (en) * | 2000-03-03 | 2007-03-15 | Temple Stephen R | Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters |
| US20080161222A1 (en) * | 2004-02-02 | 2008-07-03 | Giovanni Bozzetto S.P.A. | Use of Polyaminomethylenephosphonates as Dispersing Agents |
| US20090004288A1 (en) * | 2007-06-29 | 2009-01-01 | Collins Gary L | Stabilized ophthalmic solutions |
| US20090023914A1 (en) * | 2007-05-01 | 2009-01-22 | Alessandro Pontiroli | Process for preparing drospirenone and intermediate thereof |
| US20090054863A1 (en) * | 2003-09-23 | 2009-02-26 | Zheng Tan | Chemical activation and refining of southern pine kraft fibers |
| WO2009147327A1 (en) * | 2008-06-05 | 2009-12-10 | Laboratoires Anios | Composition for disinfection and decontamination of bodies contaminated by prions and conventional transmissible agents |
| WO2010147812A1 (en) * | 2009-06-15 | 2010-12-23 | Arkema Inc. | Alkaline peroxide treatment of rejects in an integrated neutral-alkaline paper mill |
| US8138106B2 (en) | 2005-09-30 | 2012-03-20 | Rayonier Trs Holdings Inc. | Cellulosic fibers with odor control characteristics |
| US8282774B2 (en) | 2005-05-02 | 2012-10-09 | International Paper Company | Ligno cellulosic materials and the products made therefrom |
| US8765652B2 (en) | 2004-03-05 | 2014-07-01 | Gen-Probe Incorporated | Method of making a formulation for deactivating nucleic acids |
| US8778136B2 (en) | 2009-05-28 | 2014-07-15 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9512563B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Surface treated modified cellulose from chemical kraft fiber and methods of making and using same |
| US9511167B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9512237B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Method for inhibiting the growth of microbes with a modified cellulose fiber |
| US9951470B2 (en) | 2013-03-15 | 2018-04-24 | Gp Cellulose Gmbh | Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same |
| US10138598B2 (en) | 2013-03-14 | 2018-11-27 | Gp Cellulose Gmbh | Method of making a highly functional, low viscosity kraft fiber using an acidic bleaching sequence and a fiber made by the process |
| WO2019165582A1 (en) * | 2018-02-27 | 2019-09-06 | Kemira Oyj | Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition |
| US10525410B2 (en) | 2013-01-22 | 2020-01-07 | Stephen R. Temple | Methods and equipment for treatment of odorous gas steams |
| WO2020028655A1 (en) * | 2018-08-02 | 2020-02-06 | Evonik Corporation | Polymer-stabilized aqueous hydrogen peroxide solutions and associated methods |
| US10865519B2 (en) | 2016-11-16 | 2020-12-15 | Gp Cellulose Gmbh | Modified cellulose from chemical fiber and methods of making and using the same |
| US10881756B2 (en) | 2012-06-28 | 2021-01-05 | Stephen R. Temple | Methods and equipment for treatment of odorous gas streams from industrial plants |
| US10898852B2 (en) | 2016-08-15 | 2021-01-26 | Stephen R. Temple | Processes for removing a nitrogen-based compound from a gas or liquid stream to produce a nitrogen-based product |
| CN112533864A (en) * | 2018-08-02 | 2021-03-19 | 赢创有限公司 | Method for producing stabilized aqueous hydrogen peroxide solution |
| US11332886B2 (en) | 2017-03-21 | 2022-05-17 | International Paper Company | Odor control pulp composition |
| US11389763B2 (en) | 2019-08-28 | 2022-07-19 | Stephen R. Temple | Methods for absorbing a targeted compound from a gas stream for subsequent processing or use |
| EP4110987A4 (en) * | 2020-02-28 | 2024-03-06 | Sixring Inc | Modified alkylsulfonic acid and uses thereof |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8826431D0 (en) * | 1988-11-11 | 1988-12-14 | Albright & Wilson | Phosphate composition |
| JP2602563B2 (en) * | 1989-12-15 | 1997-04-23 | 花王株式会社 | Liquid oxygen bleach composition |
| GB9007232D0 (en) * | 1990-03-30 | 1990-05-30 | Monsanto Europe Sa | Method for the preparation and/or maintenance of alkaline bleaching baths and hydrogen peroxide solutions for use therein |
| US5057228A (en) * | 1990-04-16 | 1991-10-15 | Baker Hughes Incorporated | Metal ion complexes for use as scale inhibitors |
| US5207919A (en) * | 1990-04-16 | 1993-05-04 | Baker Hughes Incorporated | Metal ion complexes for use as scale inhibitors |
| DE4416208A1 (en) * | 1994-05-07 | 1995-11-09 | Henkel Kgaa | Use of phosphorus-free, water-soluble polymers and polyhydroxy mono- or dicarboxylates to stabilize alkaline earth metal silicates in textile bleaching |
| JPH10140192A (en) * | 1996-11-05 | 1998-05-26 | Hoechst Ind Kk | Bleaching liquid containing hydrogen peroxide and method of bleaching by using the liquid |
| WO2010053916A2 (en) | 2008-11-04 | 2010-05-14 | Sterling Lc | Method and device for wavelength shifted imaging |
| GB0901207D0 (en) | 2009-01-26 | 2009-03-11 | Innospec Ltd | Chelating agents and methods relating thereto |
| WO2011041720A2 (en) | 2009-10-01 | 2011-04-07 | Jacobsen Stephen C | Method and apparatus for manipulating movement of a micro-catheter |
| JP7061758B2 (en) * | 2018-07-11 | 2022-05-02 | 中部キレスト株式会社 | Hydrogen peroxide stabilizer and hydrogen peroxide composition |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3122417A (en) * | 1959-06-03 | 1964-02-25 | Henkel & Cie Gmbh | Stabilizing agent for peroxy-compounds and their solutions |
| US3234140A (en) * | 1964-06-05 | 1966-02-08 | Monsanto Co | Stabilization of peroxy solutions |
| GB1234320A (en) * | 1968-11-02 | 1971-06-03 | ||
| US3701825A (en) * | 1970-10-23 | 1972-10-31 | Fmc Corp | Stabilization of hydrogen peroxide with ethylenediamine tetra (methylenephosphonic acid) |
| US3860391A (en) * | 1972-03-10 | 1975-01-14 | Benckiser Knapsack Gmbh | Bleaching of cellulose containing textile fiber material with a silicate-free stabilized peroxide bleaching bath |
| US4238282A (en) * | 1979-07-23 | 1980-12-09 | Nalco Chemical Company | Chemical treatments in bleaching stages which increase pulp brightness |
| US4239643A (en) * | 1979-01-02 | 1980-12-16 | Monsanto Company | Peroxide stabilization |
| US4294575A (en) * | 1979-01-02 | 1981-10-13 | Monsanto Company | Peroxide stabilization |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2506799B2 (en) * | 1975-02-18 | 1977-03-31 | Basf Ag, 6700 Ludwigshafen | PROCESS FOR STABILIZING PEROXIDE STABILIZERS CONTAINING PEROXIDE BLEACHING FLATS CONTAINING ALKALINE, SILICATE AND EARTH ALKALIMETAL |
| US4130501A (en) * | 1976-09-20 | 1978-12-19 | Fmc Corporation | Stable viscous hydrogen peroxide solutions containing a surfactant and a method of preparing the same |
| US4132762A (en) * | 1977-10-31 | 1979-01-02 | Shell Oil Company | Hydrogen peroxide stabilization |
| GB2033937B (en) * | 1978-09-27 | 1983-07-27 | Unilever Ltd | Bleaching and cleaning composition |
| US4333844A (en) * | 1979-11-12 | 1982-06-08 | Lever Brothers Company | Detergent compositions |
| FR2476684A1 (en) * | 1980-02-21 | 1981-08-28 | Interox | PROCESS FOR INHIBITING CORROSION OF TITANIUM APPLIANCES |
| GB8312185D0 (en) * | 1983-05-04 | 1983-06-08 | Unilever Plc | Bleaching and cleaning composition |
| EP0137669B1 (en) * | 1983-08-27 | 1988-07-06 | The Procter & Gamble Company | Detergent compositions |
| DE3423452A1 (en) * | 1984-06-26 | 1986-01-02 | Sandoz-Patent-GmbH, 7850 Lörrach | Stabilising mixture for the peroxide bleaching of cellulose-containing materials |
-
1984
- 1984-12-24 US US06/686,111 patent/US4614646A/en not_active Expired - Lifetime
-
1985
- 1985-12-04 CA CA000496865A patent/CA1235881A/en not_active Expired
- 1985-12-06 AR AR302499A patent/AR240302A1/en active
- 1985-12-10 EP EP85308960A patent/EP0186990B1/en not_active Expired - Lifetime
- 1985-12-10 DE DE8585308960T patent/DE3584669D1/en not_active Expired - Fee Related
- 1985-12-12 NZ NZ214537A patent/NZ214537A/en unknown
- 1985-12-16 AU AU51256/85A patent/AU576280B2/en not_active Ceased
- 1985-12-19 ZA ZA859707A patent/ZA859707B/en unknown
- 1985-12-23 FI FI855151A patent/FI79825C/en not_active IP Right Cessation
- 1985-12-23 BR BR8506446A patent/BR8506446A/en not_active IP Right Cessation
- 1985-12-23 JP JP60288047A patent/JPS61155208A/en active Granted
- 1985-12-23 DK DK604285A patent/DK167491B1/en active
- 1985-12-23 NO NO855253A patent/NO168940C/en unknown
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3122417A (en) * | 1959-06-03 | 1964-02-25 | Henkel & Cie Gmbh | Stabilizing agent for peroxy-compounds and their solutions |
| US3234140A (en) * | 1964-06-05 | 1966-02-08 | Monsanto Co | Stabilization of peroxy solutions |
| GB1234320A (en) * | 1968-11-02 | 1971-06-03 | ||
| US3701825A (en) * | 1970-10-23 | 1972-10-31 | Fmc Corp | Stabilization of hydrogen peroxide with ethylenediamine tetra (methylenephosphonic acid) |
| US3860391A (en) * | 1972-03-10 | 1975-01-14 | Benckiser Knapsack Gmbh | Bleaching of cellulose containing textile fiber material with a silicate-free stabilized peroxide bleaching bath |
| US4239643A (en) * | 1979-01-02 | 1980-12-16 | Monsanto Company | Peroxide stabilization |
| US4294575A (en) * | 1979-01-02 | 1981-10-13 | Monsanto Company | Peroxide stabilization |
| US4238282A (en) * | 1979-07-23 | 1980-12-09 | Nalco Chemical Company | Chemical treatments in bleaching stages which increase pulp brightness |
Cited By (99)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5180514A (en) * | 1985-06-17 | 1993-01-19 | The Clorox Company | Stabilizing system for liquid hydrogen peroxide compositions |
| US4744968A (en) * | 1985-09-03 | 1988-05-17 | Technicon Instruments Corporation | Stabilized aqueous hydrogen peroxide solution |
| US4959075A (en) * | 1985-12-23 | 1990-09-25 | Henkel Kommanditgesellschaft Auf Aktien | Silicate- and magnesium-free stabilizer hydrogen peroxide mixtures for bleaching processes |
| US4880566A (en) * | 1985-12-23 | 1989-11-14 | Henkel Kommanditgesellschaft Auf Aktien | Silicate-and magnesium-free stabilizer mixtures |
| AU600756B2 (en) * | 1986-09-15 | 1990-08-23 | Dow Chemical Company, The | Improved process for the bleaching of cellulosic pulps using hydrogen peroxide |
| US4732650A (en) * | 1986-09-15 | 1988-03-22 | The Dow Chemical Company | Bleaching of cellulosic pulps using hydrogen peroxide |
| US4889689A (en) * | 1986-10-14 | 1989-12-26 | Ciba-Geigy Corporation | Method of disinfecting a soft contact lens with a diethylene triamine penta(methylenephosphonic acid) stabilized hydrogen peroxide solution |
| US4963157A (en) * | 1987-04-17 | 1990-10-16 | Nippon Peroxide Co., Ltd. | Method for bleaching cellulosic fiber material with hydrogen peroxide |
| US4849198A (en) * | 1987-06-19 | 1989-07-18 | Degussa Aktiengesellschaft | Method of reducing the tendency of particulate active oxygen compounds to cake |
| US5102575A (en) * | 1988-06-13 | 1992-04-07 | Atochem | Stabilization of H2 O2 bleaching and bleaching/desizing baths |
| US5576028A (en) * | 1988-08-04 | 1996-11-19 | Ciba Geigy Corporation | Method of preserving ophthalmic solutions and compositions therefor |
| US5607698A (en) * | 1988-08-04 | 1997-03-04 | Ciba-Geigy Corporation | Method of preserving ophthalmic solution and compositions therefor |
| US5725887A (en) * | 1988-08-04 | 1998-03-10 | Ciba Vision Corporation | Method of preserving ophthalmic solutions and compositions therefor |
| US5130053A (en) * | 1989-11-09 | 1992-07-14 | Interox Chemicals Limited | Stabilization of concentrated hydrogen peroxide solutions |
| US5013404A (en) * | 1989-11-15 | 1991-05-07 | The Dow Chemical Company | Process for alkaline peroxide bleaching of wood pulp using a quaternary amine as additive |
| US5145558A (en) * | 1989-11-15 | 1992-09-08 | The Dow Chemical Company | Composition for alkaline peroxide bleaching of wood pulp using a quaternary amine as additive |
| DE4035813A1 (en) * | 1990-11-10 | 1992-05-14 | Akzo Gmbh | OXYGEN BLEACHING |
| US5322647A (en) * | 1990-11-10 | 1994-06-21 | Akzo N.V. | Oxygen bleaching of cotton linters by disproportionation of hydrogen peroxide |
| US5302311A (en) * | 1991-02-28 | 1994-04-12 | Mitsubishi Gas Chemical Company, Inc. | Cleaning solution of semiconductor substrate |
| US5205907A (en) * | 1991-11-25 | 1993-04-27 | Macmillan Bloedel Limited | Removal of manganese from pulp using a chelating agent and magnesium sulphate |
| US5223091A (en) * | 1991-11-25 | 1993-06-29 | Macmillan Bloedel Limited | Method of brightening mechanical pulp using silicate-free peroxide bleaching |
| US5248389A (en) * | 1992-03-18 | 1993-09-28 | Fmc Corporation | Process for peroxide bleaching of mechanical pulp using sodium carbonate and non-silicate chelating agents |
| WO1994012438A1 (en) * | 1992-11-24 | 1994-06-09 | Akzo Nobel N.V. | Scale inhibiting composition |
| US5292449A (en) * | 1992-11-24 | 1994-03-08 | Akzo Nv | Scale inhibiting composition |
| WO1995029216A1 (en) * | 1994-04-20 | 1995-11-02 | The Procter & Gamble Company | Detergent powder compositions comprising metal ion-chelant complex and anionic functional polymer |
| US5780419A (en) * | 1994-04-20 | 1998-07-14 | The Procter & Gamble Company | Detergent powder compositions comprising metal ion-chelant complex and anionic functional polymer |
| WO1999009244A1 (en) * | 1997-08-14 | 1999-02-25 | Takashi Watanabe | Chemical method for lignin depolymerization |
| US6214976B1 (en) | 1997-08-14 | 2001-04-10 | T. Watababe | Chemical method for lignin depolymerization |
| US6120554A (en) * | 1998-02-02 | 2000-09-19 | American Renewable Resources Llc | Catalyzed alkaline hydrogen peroxide bleaching of dye-containing cellulose textiles |
| US7112309B2 (en) | 2000-03-03 | 2006-09-26 | Steen Research Llc | Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters |
| US6645450B2 (en) * | 2000-03-03 | 2003-11-11 | Steen Research, Llc | Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters |
| US20070059229A1 (en) * | 2000-03-03 | 2007-03-15 | Temple Stephen R | Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters |
| US20040115112A1 (en) * | 2000-03-03 | 2004-06-17 | Steen Research Llc | Method and apparatus for use of reacted hydrogen peroxide compounds in industrial process waters |
| FR2820034A1 (en) * | 2001-01-26 | 2002-08-02 | Oreal | OXIDIZING COMPOSITION FOR THE TREATMENT OF KERATINIC MATERIALS COMPRISING A CATIONIC POLY (VINYLLACTAM) |
| WO2002058660A1 (en) * | 2001-01-26 | 2002-08-01 | L'oreal | Oxidising composition for the treatment of keratin comprising a cationic poly(vinyllactam) |
| US20070092582A1 (en) * | 2002-01-18 | 2007-04-26 | Fu-Pao Tsao | Methods of preserving ophthalmic solutions and preserved ophthalmic solutions |
| US20110135752A1 (en) * | 2002-01-18 | 2011-06-09 | Fu-Pao Tsao | Methods For Preserving Ophthalmic Solutions and Preserved Ophthalmic Solutions |
| WO2003059069A1 (en) * | 2002-01-18 | 2003-07-24 | Novartis Ag | Methods for preserving ophthalmic solutions and preserved ophtalmic solutions |
| US20040129295A1 (en) * | 2002-11-22 | 2004-07-08 | Lovetro David C. | Chemical composition and method |
| US20040101461A1 (en) * | 2002-11-22 | 2004-05-27 | Lovetro David C. | Chemical composition and method |
| US7459005B2 (en) * | 2002-11-22 | 2008-12-02 | Akzo Nobel N.V. | Chemical composition and method |
| US8262850B2 (en) | 2003-09-23 | 2012-09-11 | International Paper Company | Chemical activation and refining of southern pine kraft fibers |
| US20090054863A1 (en) * | 2003-09-23 | 2009-02-26 | Zheng Tan | Chemical activation and refining of southern pine kraft fibers |
| US7659315B2 (en) | 2004-02-02 | 2010-02-09 | Giovanni Bozzetto S.P.A. | Use of polyaminomethylenephosphonates as dispersing agents |
| US20080161222A1 (en) * | 2004-02-02 | 2008-07-03 | Giovanni Bozzetto S.P.A. | Use of Polyaminomethylenephosphonates as Dispersing Agents |
| US9371556B2 (en) | 2004-03-05 | 2016-06-21 | Gen-Probe Incorporated | Solutions, methods and kits for deactivating nucleic acids |
| US8765652B2 (en) | 2004-03-05 | 2014-07-01 | Gen-Probe Incorporated | Method of making a formulation for deactivating nucleic acids |
| US20050217813A1 (en) * | 2004-03-31 | 2005-10-06 | Shevchenko Sergey M | Methods to enhance brightness of pulp and optimize use of bleaching chemicals |
| US7351764B2 (en) * | 2004-03-31 | 2008-04-01 | Nalco Company | Methods to enhance brightness of pulp and optimize use of bleaching chemicals |
| US8753484B2 (en) | 2005-05-02 | 2014-06-17 | International Paper Company | Ligno cellulosic materials and the products made therefrom |
| US10907304B2 (en) | 2005-05-02 | 2021-02-02 | International Paper Company | Ligno cellulosic materials and the products made therefrom |
| US8282774B2 (en) | 2005-05-02 | 2012-10-09 | International Paper Company | Ligno cellulosic materials and the products made therefrom |
| US20070048389A1 (en) * | 2005-08-26 | 2007-03-01 | Fu-Pao Tsao | Stabilized and preserved ketotifen ophthalmic compositions |
| US20080207692A1 (en) * | 2005-08-26 | 2008-08-28 | Fu-Pao Tsao | Stabilized and preserved ketoifen ophthalmic compositions |
| US20110028516A1 (en) * | 2005-08-26 | 2011-02-03 | Fu-Pao Tsao | Stabilized and preserved ketoifen ophthalmic compositions |
| US20070048388A1 (en) * | 2005-08-26 | 2007-03-01 | Fu-Pao Tsao | Stabilized and preserved ketotifen ophthalmic compositions |
| US20080193558A1 (en) * | 2005-08-26 | 2008-08-14 | Fu-Pao Tsao | Stabilized and preserved ketotifen ophth almic compositions |
| US8574683B2 (en) | 2005-09-30 | 2013-11-05 | Rayonier Trs Holdings, Inc. | Method of making a pulp sheet of odor-inhibiting absorbent fibers |
| US8138106B2 (en) | 2005-09-30 | 2012-03-20 | Rayonier Trs Holdings Inc. | Cellulosic fibers with odor control characteristics |
| US20090023914A1 (en) * | 2007-05-01 | 2009-01-22 | Alessandro Pontiroli | Process for preparing drospirenone and intermediate thereof |
| US20090004288A1 (en) * | 2007-06-29 | 2009-01-01 | Collins Gary L | Stabilized ophthalmic solutions |
| WO2009147327A1 (en) * | 2008-06-05 | 2009-12-10 | Laboratoires Anios | Composition for disinfection and decontamination of bodies contaminated by prions and conventional transmissible agents |
| CN102112159A (en) * | 2008-06-05 | 2011-06-29 | 安尼奥斯实验室 | Composition for disinfection and decontamination of bodies contaminated by prions and conventional transmissible agents |
| FR2932093A1 (en) * | 2008-06-05 | 2009-12-11 | Anios Lab Sarl | COMPOSITION FOR SIMULTANEOUS DISINFECTION AND DECONTAMINATION OF CONTAMINATED BODIES BY CONVENTIONAL (ATC) AND UNCONVENTIONAL TRANSMISSIBLE AGENTS (ATNC). |
| CN102112159B (en) * | 2008-06-05 | 2015-01-14 | 安尼奥斯实验室 | Composition for disinfection and decontamination of bodies contaminated by prions and conventional transmissible agents |
| US9512561B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9909257B2 (en) | 2009-05-28 | 2018-03-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9511167B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9512237B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Method for inhibiting the growth of microbes with a modified cellulose fiber |
| US9512562B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US10731293B2 (en) | 2009-05-28 | 2020-08-04 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9777432B2 (en) | 2009-05-28 | 2017-10-03 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9512563B2 (en) | 2009-05-28 | 2016-12-06 | Gp Cellulose Gmbh | Surface treated modified cellulose from chemical kraft fiber and methods of making and using same |
| US9926666B2 (en) | 2009-05-28 | 2018-03-27 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| USRE49570E1 (en) | 2009-05-28 | 2023-07-04 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US9970158B2 (en) | 2009-05-28 | 2018-05-15 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US10106927B2 (en) | 2009-05-28 | 2018-10-23 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US11111628B2 (en) | 2009-05-28 | 2021-09-07 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| US8778136B2 (en) | 2009-05-28 | 2014-07-15 | Gp Cellulose Gmbh | Modified cellulose from chemical kraft fiber and methods of making and using the same |
| WO2010147812A1 (en) * | 2009-06-15 | 2010-12-23 | Arkema Inc. | Alkaline peroxide treatment of rejects in an integrated neutral-alkaline paper mill |
| US10881756B2 (en) | 2012-06-28 | 2021-01-05 | Stephen R. Temple | Methods and equipment for treatment of odorous gas streams from industrial plants |
| US10525410B2 (en) | 2013-01-22 | 2020-01-07 | Stephen R. Temple | Methods and equipment for treatment of odorous gas steams |
| US10138598B2 (en) | 2013-03-14 | 2018-11-27 | Gp Cellulose Gmbh | Method of making a highly functional, low viscosity kraft fiber using an acidic bleaching sequence and a fiber made by the process |
| US10174455B2 (en) | 2013-03-15 | 2019-01-08 | Gp Cellulose Gmbh | Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same |
| US10550516B2 (en) | 2013-03-15 | 2020-02-04 | Gp Cellulose Gmbh | Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same |
| US10753043B2 (en) | 2013-03-15 | 2020-08-25 | Gp Cellulose Gmbh | Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same |
| US10294614B2 (en) | 2013-03-15 | 2019-05-21 | Gp Cellulose Gmbh | Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same |
| US9951470B2 (en) | 2013-03-15 | 2018-04-24 | Gp Cellulose Gmbh | Low viscosity kraft fiber having an enhanced carboxyl content and methods of making and using the same |
| US10898852B2 (en) | 2016-08-15 | 2021-01-26 | Stephen R. Temple | Processes for removing a nitrogen-based compound from a gas or liquid stream to produce a nitrogen-based product |
| US10865519B2 (en) | 2016-11-16 | 2020-12-15 | Gp Cellulose Gmbh | Modified cellulose from chemical fiber and methods of making and using the same |
| US11332886B2 (en) | 2017-03-21 | 2022-05-17 | International Paper Company | Odor control pulp composition |
| US11613849B2 (en) | 2017-03-21 | 2023-03-28 | International Paper Company | Odor control pulp composition |
| WO2019165582A1 (en) * | 2018-02-27 | 2019-09-06 | Kemira Oyj | Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition |
| US11498859B2 (en) | 2018-02-27 | 2022-11-15 | Kermira Oyj | Composition and method for stabilizing iron compounds in an aqueous environment, and use of composition |
| CN112533865A (en) * | 2018-08-02 | 2021-03-19 | 赢创有限公司 | Polymer stabilized aqueous hydrogen peroxide solutions and related methods |
| CN112533864A (en) * | 2018-08-02 | 2021-03-19 | 赢创有限公司 | Method for producing stabilized aqueous hydrogen peroxide solution |
| WO2020028655A1 (en) * | 2018-08-02 | 2020-02-06 | Evonik Corporation | Polymer-stabilized aqueous hydrogen peroxide solutions and associated methods |
| US11389763B2 (en) | 2019-08-28 | 2022-07-19 | Stephen R. Temple | Methods for absorbing a targeted compound from a gas stream for subsequent processing or use |
| EP4110987A4 (en) * | 2020-02-28 | 2024-03-06 | Sixring Inc | Modified alkylsulfonic acid and uses thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3584669D1 (en) | 1991-12-19 |
| AR240302A1 (en) | 1990-03-30 |
| AU576280B2 (en) | 1988-08-18 |
| FI79825B (en) | 1989-11-30 |
| CA1235881A (en) | 1988-05-03 |
| NO168940C (en) | 1992-04-29 |
| NO168940B (en) | 1992-01-13 |
| DK604285A (en) | 1986-06-25 |
| EP0186990A3 (en) | 1987-11-19 |
| FI855151A (en) | 1986-06-25 |
| EP0186990B1 (en) | 1991-11-13 |
| NZ214537A (en) | 1989-08-29 |
| DK167491B1 (en) | 1993-11-08 |
| EP0186990A2 (en) | 1986-07-09 |
| AU5125685A (en) | 1986-07-03 |
| DK604285D0 (en) | 1985-12-23 |
| ZA859707B (en) | 1987-08-26 |
| JPS61155208A (en) | 1986-07-14 |
| FI855151A0 (en) | 1985-12-23 |
| NO855253L (en) | 1986-06-25 |
| FI79825C (en) | 1990-03-12 |
| BR8506446A (en) | 1986-09-02 |
| JPH0549602B2 (en) | 1993-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4614646A (en) | Stabilization of peroxide systems in the presence of alkaline earth metal ions | |
| US4732650A (en) | Bleaching of cellulosic pulps using hydrogen peroxide | |
| CA1106574A (en) | Stabilisation of hydrogen peroxide | |
| US4238282A (en) | Chemical treatments in bleaching stages which increase pulp brightness | |
| JP2012524172A5 (en) | ||
| EP0801032B1 (en) | Stabilizers for additives in aqueous systems containing ozone | |
| US5464563A (en) | Bleaching composition | |
| US5616280A (en) | Bleaching composition | |
| US5013404A (en) | Process for alkaline peroxide bleaching of wood pulp using a quaternary amine as additive | |
| US2988514A (en) | Bleaching composition and method | |
| US4752354A (en) | Process and composition for bleaching wood pulp | |
| US4089893A (en) | 2,2,2-Tris(hydroxymethyl)ethylphosponic acid and method for its preparation | |
| US5145558A (en) | Composition for alkaline peroxide bleaching of wood pulp using a quaternary amine as additive | |
| EP0369711B1 (en) | Phosphate composition and uses thereof | |
| JPH07109107A (en) | Stabilizing agent for aqueous solution of hypochlorite | |
| JP2533104B2 (en) | Oxidative bleaching method of groundwood pulp | |
| EP1276744A1 (en) | N-alpha , n-omega -dialkyl aminomethylenephosphonic acids and use thereof | |
| EP0449797A1 (en) | Method for the preparation and/or maintenance of alkaline bleaching baths and hydrogen peroxide solutions for use therein | |
| US3829358A (en) | Groundwood pulp bleaching with sodium hydrosulfite containing diglycolates | |
| KR100482289B1 (en) | Stabilizer composition useful for peroxide bleaching and method for stabilizing peroxide bleaching agent | |
| JPH0437197B2 (en) | ||
| DE19849379A1 (en) | Aqueous solutions of phosphonic acids |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: DOW CHEMICAL COMPANY THE, Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CHRISTIANSEN, STEVEN H.;REEL/FRAME:004561/0700 Effective date: 19841219 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |
|
| FEPP | Fee payment procedure |
Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 4 |
|
| REFU | Refund |
Free format text: REFUND PROCESSED. MAINTENANCE FEE TENDERED TOO EARLY (ORIGINAL EVENT CODE: R161); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY |
|
| FPAY | Fee payment |
Year of fee payment: 8 |
|
| FPAY | Fee payment |
Year of fee payment: 12 |